EP0878502A2 - Formulations de Vitamine E pour la stabilisastion de matériaux polymères organiques - Google Patents

Formulations de Vitamine E pour la stabilisastion de matériaux polymères organiques Download PDF

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Publication number
EP0878502A2
EP0878502A2 EP98810372A EP98810372A EP0878502A2 EP 0878502 A2 EP0878502 A2 EP 0878502A2 EP 98810372 A EP98810372 A EP 98810372A EP 98810372 A EP98810372 A EP 98810372A EP 0878502 A2 EP0878502 A2 EP 0878502A2
Authority
EP
European Patent Office
Prior art keywords
tert
butyl
bis
hydroxy
und
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP98810372A
Other languages
German (de)
English (en)
Inventor
Rita Pitteloud
Christoph Kröhnke
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Novartis AG
BASF Schweiz AG
Original Assignee
Ciba Geigy AG
Ciba Spezialitaetenchemie Holding AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ciba Geigy AG, Ciba Spezialitaetenchemie Holding AG filed Critical Ciba Geigy AG
Publication of EP0878502A2 publication Critical patent/EP0878502A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1545—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

Definitions

  • the invention relates to a composition which A) is a polymeric material, B) is a Stabilizer mixture of ⁇ - tocopherol, a solid polyhydroxy compound and / or a Contains acid binding compound. Further objects of the invention are Stabilizer mixture as such and its use for stabilizing polymers, especially of food packaging.
  • a disadvantage of the polyhydroxy compounds mentioned there is that they are liquid or low-melting compounds which, together with ⁇ -tocopherol, which is itself an oily material with a melting point of 2.5-3.5 ° C, an oily to greasy pasty composition result.
  • oils or pastes are for incorporation into polymer granules, for example only poorly suited because they stick to the walls of the storage and mixing containers stay. This can lead to inhomogeneous distributions during extrusion.
  • the present invention provides such stabilizer mixtures that are compatible with organic polymeric materials give solid compositions, which without oily in the extruder To leave deposits that can be processed.
  • the mixing is completely homogeneous and it results very well against heat stabilized polymers.
  • By adding the selected polyhydroxy compounds achieves a particularly low yellowing during the thermal processes. A sweat of the polyhydroxy compounds or volatilization due to a low Vapor pressure is not to be feared with these connections. Since they are completely in Polymer remain contained, they also develop their full effectiveness.
  • the polymers stabilized in this way are particularly suitable for food packaging.
  • the invention relates to a composition
  • a composition comprising A) an organic one polymeric material and B) a stabilizer mixture consisting of b1) of ⁇ -tocopherol, b2) from a solid polyhydroxy compound, which is selected from the group consisting of from triglycerol, ditrimethylolpropane, dipentaerythritol, tripentaerythritol, D-mannitol, D-sorbitol and xylitol or b3) from an acid-binding material or a mixture of the components b2) and b3).
  • the polymeric organic material A) is preferably a polyolefin, polystyrene, PVC, polyamide, Polyacrylate or polyester. It is particularly preferably a polyolefin, especially polyethylene or polypropylene
  • the solid polyhydroxy compound is preferably ditrimethylolpropane, dipentaerythritol or Tripentaerythritol.
  • the polymeric composition can be in addition to or instead of Polyhydroxy compound b2) contain an acid-binding material
  • An alkaline earth metal or zinc salt of a C 3 -C 18 carboxylic acid, an alkaline earth metal / aluminum carbonate, hydroxyborate, hydroxyphosphite or a zeolite is preferably used as the acid-binding material.
  • Alkaline earth metal or Zn salts of a C 3 -C 18 carboxylic acid are particularly preferred.
  • the carboxylic acid can be saturated or unsaturated, branched or unbranched. They are preferably monocarboxylic acids, which, however, can be substituted by one or more OH groups.
  • saturated C 3 -C 18 carboxylic acids are propionic acid, butyric acid, valeric acid, caproic acid, palmitic acid, stearic acid, lauric acid or lactic acid.
  • Lactic acid, lauric acid and stearic acid are particularly preferred.
  • a composition containing A) is an organic polymeric material and B) a stabilizer mixture consisting of b1) of ⁇ -tocopherol and b2) of a solid Polyhydroxy compound which is selected from the group consisting of triglycerol, Ditrimethylolpropane, dipentaerythritol, tripentaerythritol, D-mannitol, D-sorbitol and xylitol.
  • Component b1) is preferred in an amount of 0.005 to 2% by weight, based on the Polymer included.
  • Component b2) is preferred in an amount of 0.005 to 5% by weight, based on the Polymer included.
  • the ratio b1) to b2) is preferably from 10: 1 to 1:10.
  • Component b3) is preferably in an amount of 0.005 to 5% based on the Polymer included.
  • UV absorber or a sterically hindered amine or both are preferred available.
  • UV absorbers and sterically hindered amines are given above specified.
  • Another object of the invention is a stabilizer mixture consisting of b1) of ⁇ -tocopherol, b2) from a solid polyhydroxy compound, which is selected from the Group consisting of triglycerol, ditrimethylolpropane, dipentaerythritol, tripentaerythritol, D-mannitol, D-sorbitol and xylitol or b3) from an acid-binding material or one Mixture of components b2) and b3).
  • components b1) to b3) the meanings given above, including their preferences, apply.
  • the mixing of the stabilizer mixture can be carried out by means of devices such as mixers, kneaders or the like which are customary in the art
  • Suitable solvents are ethers, esters, ketones, amides or hydrocarbons.
  • the mixture of the stabilizer mixture with the polymer can, for example, by Mixing in of the compounds and optionally other additives according to those in the art usual methods.
  • the incorporation can take place before or during the shaping respectively.
  • the components can be added together or in any order will.
  • Polymer compositions according to the invention can be used in various forms or processed into different products, e.g. B. as (to) films, fibers, Wristbands, molding compounds or profiles.
  • a stabilizer mixture B for the thermal stabilization of organic polymers, in particular for thermal Stabilization of food packaging.
  • Mixtures 103-108 are made according to the procedure described in Example 1 produced.
  • Mixtures 116-126 are obtained by the method described in Example 4.
  • a solution of 4 g is added to a solution of vitamin E (1 g) in 40 ml of ethyl acetate Ditrimetholpropane added in 18 ml of methanol and 5 g of calcium stearate.
  • the received Suspension is stirred for 2 hours at room temperature. Then be the solvents are distilled off and the solid residue is dried under high vacuum. It 10 g of the desired mixture 130 are obtained as a white powder.
  • Vitamin E / solid polyhydroxy compounds (color improvers) mixture Color enhancer Color ratio Vit E Mp ° C 101 Ditrimethylol propane 4: 1 107 102 Ditrimethylol propane 4: 1 107 103 Dipentaerythritol 4: 1 221 104 Dipentaerythritol 3: 1 185-218 105 Tripentaerythritol 4: 1 238 106 Mannitol 4: 1 171 107 Sorbitol 4: 1 97 108 Ditrimethylol propane 3: 1 107-110 109 Ditrimethylol propane 2: 1 103 110 Ditrimethylol propane 1: 1 107-109 111 Mannitol 3: 1 165-167 112 Sorbitol 3: 1 96 113 Sorbitol 2: 1 92-95 Vitamin E / acid scavenger blends mixture Acid scavenger Acid scavenger ratio: Vit E Mp
  • PE-HD unstabilized HD polyethylene
  • Eltex A 60-70 from Solvay
  • the temperature at the intake is 220 ° C, 230 ° C in zone 2, 240 ° C in zone 3 and 240 ° C in zone 4 (nozzle).
  • the extruded material is discharged via a strand nozzle with cooling of the strand in a water bath and subsequent granulation by means of a strand granulator.
  • the extrusion described in this way is carried out five times under identical conditions, a pattern for the melt flow and yellowness measurement being taken from the first, third and fifth extrusion.
  • the yellowness measurement is carried out in a spectral photometer suitable for remission measurement with standard light C, UV filter, gloss trap and a detector at 2 ° against the primary standard barium sulfate (white, 100% remission) and against the secondary standard, a ceramic plate (84% remission) according to ASTM D1925 measured.
  • the melt value (MFR) is measured in accordance with ISO 1163. The results are shown in Table 4.
  • Example B1 The procedure is as given in Example B1, with the difference that LLDPE is used instead of HDPE (polyethylene LLD, LL 0209 AP from BP Chemicals). The results are shown in Table 5
  • the numbers of the stabilizer mixtures refer to those in Tables 1-3 specified mixtures.
  • the percentages are percentages by weight and relate to the polymer.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP98810372A 1997-05-05 1998-04-28 Formulations de Vitamine E pour la stabilisastion de matériaux polymères organiques Withdrawn EP0878502A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH104297 1997-05-05
CH1042/97 1997-05-05

Publications (1)

Publication Number Publication Date
EP0878502A2 true EP0878502A2 (fr) 1998-11-18

Family

ID=4201109

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98810372A Withdrawn EP0878502A2 (fr) 1997-05-05 1998-04-28 Formulations de Vitamine E pour la stabilisastion de matériaux polymères organiques

Country Status (4)

Country Link
EP (1) EP0878502A2 (fr)
JP (1) JPH10316870A (fr)
KR (1) KR19980086735A (fr)
CA (1) CA2236638A1 (fr)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001005781A1 (fr) * 1999-07-21 2001-01-25 Valtion Teknillinen Tutkimuskeskus Comonomere, et polymere stabilise au moyen de ce comonomere pendant la polymerisation
WO2002002687A1 (fr) * 2000-07-05 2002-01-10 Woorichem Tech Co., Ltd. Composition a base de resine de polyolefine contenant un antioxydant naturel et un thermostabilisateur sans effet nocif pour le corps humain
US6878457B2 (en) 2002-06-05 2005-04-12 Cellresin Technologies, Llc Reducing concentration of organic materials with substituted cyclodextrin compound in polyester packaging materials
US6936204B2 (en) 1999-04-29 2005-08-30 Color Matrix Europe Ltd. Thermoplastic molding compositions and polymer additives
US7759449B2 (en) 2000-12-15 2010-07-20 Wellman, Inc. Methods for introducing additives into polyethylene terephthalate
SG163478A1 (en) * 2009-01-09 2010-08-30 Sumitomo Chemical Co Polymer stabilizer
US8017673B2 (en) 2009-01-09 2011-09-13 Sumitomo Chemical Company, Limited Polymer stabilizer
DE102013005426A1 (de) * 2013-03-27 2014-10-02 Baerlocher Gmbh Stabilisatorzusammensetzungen enthaltend Salze von Dicarbonsäuren und Polyole
WO2017114782A1 (fr) * 2015-12-29 2017-07-06 Sabic Global Technologies B.V. Composition de polyoléfine stabilisée
WO2018069488A1 (fr) * 2016-10-14 2018-04-19 Sabic Global Technologies B.V. Matériau d'emballage
WO2018069540A1 (fr) * 2016-10-14 2018-04-19 Sabic Global Technologies B.V. Matériau d'emballage stérilisable
WO2020260829A1 (fr) * 2019-06-27 2020-12-30 Universite De Pau Et Du Pays De L'adour Materiau pour emballage alimentaire et son procede de préparation

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4691761B2 (ja) * 2000-08-09 2011-06-01 旭硝子株式会社 耐候性に優れた硬化性組成物
JP2005194472A (ja) * 2004-01-09 2005-07-21 Toyo Seikan Kaisha Ltd 金属板被覆用樹脂組成物、樹脂被覆金属板、缶及び缶蓋
BRPI1013940A2 (pt) * 2009-05-04 2016-04-05 Smith & Nephew Inc efeitos sinérgicos da mistura de aditivos múltiplos em uhmwpe
JP5938959B2 (ja) * 2011-10-20 2016-06-22 住友化学株式会社 樹脂組成物及びこれからなる放熱部品
WO2017168372A1 (fr) * 2016-03-30 2017-10-05 Sabic Global Technologies B.V. Systèmes de réacteur à usage unique et procédés

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6936204B2 (en) 1999-04-29 2005-08-30 Color Matrix Europe Ltd. Thermoplastic molding compositions and polymer additives
WO2001005781A1 (fr) * 1999-07-21 2001-01-25 Valtion Teknillinen Tutkimuskeskus Comonomere, et polymere stabilise au moyen de ce comonomere pendant la polymerisation
WO2002002687A1 (fr) * 2000-07-05 2002-01-10 Woorichem Tech Co., Ltd. Composition a base de resine de polyolefine contenant un antioxydant naturel et un thermostabilisateur sans effet nocif pour le corps humain
US7759449B2 (en) 2000-12-15 2010-07-20 Wellman, Inc. Methods for introducing additives into polyethylene terephthalate
US6878457B2 (en) 2002-06-05 2005-04-12 Cellresin Technologies, Llc Reducing concentration of organic materials with substituted cyclodextrin compound in polyester packaging materials
US6974603B2 (en) 2002-06-05 2005-12-13 Cellresin Technologies, Llc Reducing concentration of organic materials with substituted cyclodextrin compound in polyester packaging materials
US7018712B2 (en) 2002-06-05 2006-03-28 Cellresin Technologies, Llc Reducing concentration of organic materials with substituted cyclodextrin compound in polyester packaging materials
US8017673B2 (en) 2009-01-09 2011-09-13 Sumitomo Chemical Company, Limited Polymer stabilizer
SG163478A1 (en) * 2009-01-09 2010-08-30 Sumitomo Chemical Co Polymer stabilizer
DE102013005426A1 (de) * 2013-03-27 2014-10-02 Baerlocher Gmbh Stabilisatorzusammensetzungen enthaltend Salze von Dicarbonsäuren und Polyole
WO2017114782A1 (fr) * 2015-12-29 2017-07-06 Sabic Global Technologies B.V. Composition de polyoléfine stabilisée
WO2018069488A1 (fr) * 2016-10-14 2018-04-19 Sabic Global Technologies B.V. Matériau d'emballage
WO2018069540A1 (fr) * 2016-10-14 2018-04-19 Sabic Global Technologies B.V. Matériau d'emballage stérilisable
CN110049873A (zh) * 2016-10-14 2019-07-23 Sabic环球技术有限责任公司 可消毒的包装材料
WO2020260829A1 (fr) * 2019-06-27 2020-12-30 Universite De Pau Et Du Pays De L'adour Materiau pour emballage alimentaire et son procede de préparation
FR3097849A1 (fr) * 2019-06-27 2021-01-01 Universite De Pau Et Du Pays De L'adour Matériau pour emballage alimentaire et procédé de préparation

Also Published As

Publication number Publication date
CA2236638A1 (fr) 1998-11-05
JPH10316870A (ja) 1998-12-02
KR19980086735A (ko) 1998-12-05

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